WO2000009597A1 - Puncture-resistant polyolefin membranes - Google Patents
Puncture-resistant polyolefin membranes Download PDFInfo
- Publication number
- WO2000009597A1 WO2000009597A1 PCT/US1999/015085 US9915085W WO0009597A1 WO 2000009597 A1 WO2000009597 A1 WO 2000009597A1 US 9915085 W US9915085 W US 9915085W WO 0009597 A1 WO0009597 A1 WO 0009597A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid
- thermoplastic polymer
- melt
- polymer component
- compatible
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
- B01D71/261—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
- B01D71/262—Polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/052—Inducing phase separation by thermal treatment, e.g. cooling a solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
Definitions
- the present invention relates to puncture-resistant microporous materials (e.g , films and/or membranes)
- the invention relates to articles made from microporous materials and to methods for preparing such materials and articles
- Microporous films, sheets, and membranes are materials that have structures which enable fluids to pass readily through them These materials have pores whose effective size typically is at least several times the mean free path of the flowing molecules, namely from several micrometers down to as low as about 100 Angstroms Sheets made from the materials generally are opaque, even when made from an originally transparent material, because the surfaces and internal structure scatter visible light Microporous membranes enjoy utility in a wide range of divergent applications, including use in the filtration of solid materials, ultrafiltration of colloidal matter, use as diffusion barriers or separators in electrochemical cells and uses in the preparation of synthetic leathers and fabric laminates The latter requires the membranes to be permeable to water vapor but substantially impermeable to liquid water when used to prepare such articles as shoes, raincoats, outer wear, camping equipment, and the like Microporous membranes also are utilized in the filtration of antibiotics, beers, oils, bacteriological broths, and for the analysis of air, microbiological samples, intravenous fluids and vaccines Surgical dressings, band
- microporous membranes may be laminated onto other articles to make laminates of specialized utility
- Such laminates may include, for example, a microporous layer laminated to an outer shell layer to make a particularly useful garment material
- Microporous membranes may also be utilized as a tape backing to provide such products as vapor transmissive wound dressing or hair setting tapes and the like
- thermally induced phase separation Generally such a process is based on the use of a polymer that is soluble in a diluent at an elevated temperature but that is insoluble in the diluent material at a relatively lower temperature
- phase transition can involve a solid-liquid phase separation, a liquid-liquid phase separation or a liquid to gel phase transition Examples of such methods are described in U S Pat Nos 4,247,498, 4,539,256, 4,726,989, and 4,867,881
- the present invention provides puncture resistant microporous materials made of melt-processable semi-crystalline thermoplastic polymers These microporous materials can be produced at relatively high rates and at low cost Accordingly, in one aspect, the present invention provides a method of making microporous material, the method comprising
- thermoplastic polymer component (i) from about 25 to about 60 parts by weight of a melt-processable, semi- crystalline thermoplastic polymer component, and (ii) from about 40 to about 75 parts by weight of a second component comprising either (1 ) a compound that is miscible with the thermoplastic polymer component at a temperature above the melting temperature of the thermoplastic polymer component but that phase separates from the thermoplastic polymer component when cooled below the crystallization temperature of the thermoplastic polymer component or (2) a compatible liquid that is miscible with the thermoplastic polymer component at a temperature above the liquid-liquid phase separation temperature but that phase separates from the thermoplastic polymer component when cooled,
- thermoplastic polymer component (c) cooling the shaped material to a temperature at which phase separation occurs between the compound or compatible liquid and the thermoplastic polymer component through either (1) crystallization precipitation of the thermoplastic polymer component or (2) liquid-liquid phase separation, and
- the invention provides a microporous material comprising a melt-processable, semi-crystalline thermoplastic polymer where the thermoplastic polymer is miscible in a compound or compatible liquid when heated above the melting temperature of the thermoplastic polymer or the liquid-liquid phase separation temperature and phase separates from the compound or compatible liquid when cooled, where the material is stretched in at least two perpendicular directions to an area expansion ratio of greater than nine, and where the material has a puncture resistance of at least 350 g/25 micrometers
- Articles, including membranes, films and sheets made of the microporous materials also are described DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
- the microporous materials of the invention are made using melt-processable polymers.
- the melt-processed materials are made microporous by phase separating from the material either (1) a compound that is miscible with the thermoplastic polymer component at a temperature above the melting temperature of the thermoplastic polymer component but that phase separates from the polymer component when cooled below the crystallization temperature of the component or (2) a compatible liquid that is miscible with the thermoplastic polymer component at a temperature above the liquid-liquid phase separation temperature but that phase separates from the polymer when cooled.
- the term "normally melt processable” or simply “melt processable” is used herein to refer to polymers that are melt-processable under ordinary melt-processing conditions using conventional extrusion equipment without the need for plasticizer addition.
- melting temperature is used to refer to the temperature at or above which the polymer component in a blend with a compound or a compatible liquid will melt.
- crystallization temperature refers to the temperature at or below which the polymer component in a blend with a compound, will crystallize.
- liquid-liquid phase separation temperature is used to refer to the temperature at or below which a melt of a mixture of a polymer and a compatible liquid, i.e., a homogeneous polymer-melt, phase separates by either binodal or spinodal decomposition.
- compatible refers to a material capable of forming a fine dispersion (less than 1 micron in particle size) in a continuous matrix of a second material or capable of forming an inter-penetrating polymer network of both materials.
- Polymers useful in the present invention are normally melt-processable, and the melt-processability of many common individual polymers can be predicted from melt flow indices.
- Normally melt-proccessable polymers are those that have a sufficiently low melt viscosity, i.e., a sufficiently high melt flow index, that they can be extruded through either a single screw extruder or a twin screw extruder without the aid of plasticizing materials.
- the actual melt flow index that is suitable depends on the type of polymer.
- High density polyethylene for example, is considered melt-processable if it has a melt flow index above 4 dg/min (ASTM D1238-90b, Condition F, HLMI), and ethylene alpha-olefin copolymer and ethylene vinylalcohol copolymer are considered melt processable if they have a melt flow index above 0 5 dg/min (ASTM D1238-90b, Condition E)
- Polypropylene is considered melt-processable if it has a melt flow index above 0 2 dg/min (ASTM D1238-90b,
- Condition I Poly (ethylene chlorotrifluoro ethylene) is considered melt-processable if it has a melt flow index above 1 0 dg/min (ASTM D1238-90b, Condition J) Poly (vinylidene fluoride) is considered melt-processable if it has a melt flow index above 0 2 dg min (ASTM D1238-90b, Condition L) Polymethylpentene is considered melt-processable if it has a melt flow index above 5 dg/min (ASTM D1238-90b, Condition 260 C, 5 kg load)
- melt-processable polymers also are melt-processable
- classes of polymers with melt flow indices far below values considered melt-processable for that polymer class generally are special grades that are not normally melt-processable and must be processed using special techniques, such as ram extrusion, or must be plasticized to enable processing with a conventional extrusion equipment
- Processing the polymer grades that are not normally melt-processable with a plasticizer requires longer residence times in the extruder to obtain desirable melt homogeneity and higher concentrations of a compound or compatible liquid in the melt to reduce extruder energy requirements As a result, equipment productivity is significantly limited, the production costs increased, and dangers of thermal degradation is increased
- Useful polymers also are those that can undergo processing to impart a high biaxial orientation ratio in a manner that enhances their mechanical integrity, and are semi- crystalline in nature Orienting semi-crystalline polymers significantly improves the strength and elastic modulus in the orientation direction, and orientation of a semicrystalline polymer below its melting point results in extended chain crystals with fewer chain folds and defects
- the most effective temperature range for orienting semicrystalline polymers is between the alpha crystallization temperature of the polymer and its melting point
- the alpha crystallization temperature corresponds to a secondary transition of the polymer at which crystal sub-units can be moved within the larger crystal unit
- Preferred polymers therefore are those that exhibit an alpha transition temperature and include, for example high density polyethylene, linear low density polyethylene, ethylene alpha-olefin copolymers, polypropylene, poly (vinylidene fluoride), poly (vinyl fluoride), poly (ethylene chlorotrifluoro ethylene), polyoxymethylene, poly (ethylene oxide), ethylene vinylalcohol copolymer, and compatible blends thereof Blends of one or more
- compatible polymers may also be used in practice of the invention In case of compatible blends it is not necessary that both components exhibit an alpha crystallization temperature and if liquid-liquid phase separation is used, the minor component in the blend need not to be even semi-crystalline
- Particularly preferred polymers have melting temperatures greater than 140 °C (e.g , polypropylene) and blends of such polymers with lower temperature melting polymers
- Compatibility also affects film uniformity Cast films that are made from compatible blends by the method of this invention are transparent which confirms the uniformity on a microscopic level This uniformity is of great importance for successful post-processing films with a lesser degree of uniformity made from incompatible polymers break easily during stretching Film uniformity is also important in some applications, such as thermal shutdown battery separators, for which reliable shutdown performance on a microscopic level is desirable
- Materials useful as the second component are those that form a solution with the chosen melt-processable thermoplastic polymer or polymer mixture at an elevated temperature to form a solution but that also permit the components to phase separate when cooled.
- This second component may sometimes be referred by shorthand simply as the "blending compound” or the “diluent "
- Useful blending compound materials include (1) those mentioned as useful compounds in Shipman, U.S. Pat. No. 4,539,256, (2) those mentioned as useful compatible liquids in Kinzer, U.S Pat No.
- additional materials such as, dodecyl alcohol, hexadecyl alcohol, octadecyl alcohol, dicyclohexylphthalate, triphenyl phosphate, paraffin wax, liquid paraffin, stearyl alcohol, o- dichlorobenzene, trichlorobenzene, dibutyl sebacate, and dibenzyl ether
- Compounds suitable to make the microporous material of the invention by crystallization precipitation are liquids or solids at room temperature These compounds are also materials in which the crystallizable thermoplastic polymer will dissolve to form a solution at a temperature above the melting temperature of the thermoplastic polymer component but that will phase separate on cooling at or below the crystallization temperature of the thermoplastic polymer component These compounds preferably have a boiling point at atmospheric pressure at least as high as the melting temperature of the thermoplastic polymer Compounds having lower boiling points may be used in those instances where superatmospheric pressure may be employed to elevate the boiling point of the compound to a temperature at least as high as the melting temperature of the thermoplastic polymer component.
- polypropylene Particularly useful with polypropylene are mineral oil, dioctylphthalate, or mineral spirits Mineral oil and mineral spirits are examples of mixtures of blending compounds since they are typically blends of hydrocarbon liquids These are especially useful in some of the polymer mixture of the present invention
- a compatible liquid is used to make up the solution in the preparation of the microporous material
- the compatible liquid is a liquid or solid material at room temperature that is capable of forming a solution with the thermoplastic polymer when heated above the liquid-liquid phase separation temperature and which phase separates from the polymer by liquid-liquid phase separation, rather than crystallization precipitation, on cooling
- the compatibility of the liquid with the thermoplastic polymer can be determined by heating the polymers and the liquid to form a clear homogeneous solution If a solution of the polymers and the liquid cannot be formed at any liquid concentration, then the liquid is inappropriate for use with those polymers
- the liquid used may include compounds which are solid at room temperature but liquid at the melt temperature of the thermoplastic polymer component
- thermoplastic polymers non-polar organic liquids with similar room temperature solubility parameters generally are useful at the solution temperatures
- polar organic liquids generally are useful with polar polymers
- Blends of two or more liquids can be used as the compatible liquid as long as the selected thermoplastic polymer is soluble in the liquid blend at the liquid-liquid phase separation temperature and the solution formed separates by liquid-liquid phase separation on cooling
- One component of such compatible blends also can be a non-solvent for a selected polymer as long as it is mixed with at least one effective solvent in amounts sufficient to reduce its solvency and induce, upon cooling, liquid-liquid phase separation instead of crystallization precipitation
- the selected thermoplastic semi-crystalline polymer component is polypropylene, esters such as dibutyl phthalate, ethers such as dibenzyl ether, and blends of mineral oil and non-ionic surfactants such as PEG-
- the compatible liquid can phase separate from one component of the compatible polymer mixture by liquid-liquid phase mechanism, while phase separating from the other component of the compatible polymer mixture by crystallization precipitation
- hybrid structures form, and these structures can resemble both of the described two structures, t.e , that obtained by crystallization precipitation or liquid-liquid phase separation, respectively
- an ester such as dioctyl phthalate is particularly useful to obtain a hybrid structure
- the microporous materials of the invention may also contain, in addition to compounds described above, conventional fillers or additive materials in limited quantity so as not to interfere with the formation of the microporous material, and so as not to result in unwanted exuding of the additive
- additives may include anti-static materials, dyes, plasticizers, UV absorbers, nucleating agents, anti-oxidants, and the like
- the amount of additive is typically less than 10% of the weight of the polymeric mixture, preferably less than 2% by weight
- a melt solution may be prepared by mixing the thermoplastic polymer component and the blending compound under agitation such as that provided by an extruder and heating until the temperature of the mixture is above (1) the melting point of the polymer component, or (2) the liquid-liquid phase separation temperature of the mixture At this point the mixture becomes a melt solution or single phase
- the melt solution is prepared by mixing the polymer and blending compound or compatible liquid in a continuous mixing device such as an extruder
- the blending compound is added after the polymer component is melted Once the melt solution is
- the rate of crystallization must be sufficient to achieve the overall desired number of crystal sites
- the crystallization rate is impacted by known processing conditions, and in those cases where the rate of crystallization is excessively slow additional factors must be considered, such as increased heat transfer (i.e , faster quench rate) and/or the addition of nucleating agents
- Sufficient stretching or orientation is needed to achieve improved puncture resistance over what has been known for microporous films made with normally melt processable polymers
- the shaped material or film first is stretched biaxially, i.e.
- the film must be treated to a temperature above the alpha crystallization temperature and must be stretched enough to orient the mobile crystal structures
- the most effective temperature range for orienting semicrystalline polymers is between the alpha crystallization temperature of the polymer and its melting point
- the alpha transition temperature may reduce, allowing orientation to be carried out at a temperature below the alpha transition temperature of the pure polymer
- lamellar slip in larger crystal units, such as spherulites occurs and extended chain crystals form It is difficult to effectively orient polymers that do not have the alpha transition to any great extent because their crystal segments cannot be easily rearranged into an aligned state
- the biaxial stretching may be performed either in sequentially or simultaneously Sequential stretching is carried out by drawing the films with a length orienter and a tenter (
- the shaped material lacks air voids at this stage and achieves air voids through washing
- Microporosity is achieved by removing the blending compound or diluent through a removal step after the biaxial orientation
- the removal may be carried out by extraction or by using other known methods
- the pore size and percent void volume of stretched and washed microporous material are determined by the amount of blending compound or compatible liquid used to make it Preferably from 40 to 75 parts of a compound or from 40 to 75 parts of a compatible liquid are used per 100 parts of total composition As less blending compound or compatible liquid is used, the porosity and pore interconnectivity generally decreased As more blending compound or compatible liquid is used, the porosity and pore interconnectivity generally increase, but mechanical properties (e.g , tensile properties and puncture resistance) generally decrease Porosity, pore interconnectivity, and mechanical properties are, however, also influenced to some extent by polymer types, component concentration, processing conditions (e g , quenching rate and/or stretching temperature) and by the presence or absence of a nucleating agent Thus, judicious selection of polymer materials and concentrations, blending compound or compatible liquid concentrations, and processing conditions will result in desired porosity, pore interconnectivity, and mechanical properties
- the microporous film can be thermally annealed after removal of the blending compound or compatible liquid to achieve improved dimensional stability
- the microporous material or film may be imbibed with various fillers to provide any of a variety of specific functions, thereby providing unique articles
- the imbibing material or filler may be a liquid, solvent solution, solvent dispersion or solid
- Such filler may be imbibed by any of a number of known methods which results in the deposition of such fillers within the porous structure of the microporous sheet
- imbibing materials are merely physically placed within the microporous sheet In some instances, the use of two or more reactive components as the imbibing materials permits a reaction within the microporous sheet structure
- imbibing material include antistatic agents, surfactants, and solid particulate material such as activated carbon and pigments
- a multi-layer microporous material or film of the present invention may be made employing the above-described microporous material as a layer with at least one additional porous layer
- the above-described porous layer is preferably the center layer sandwiched by, i.e., in between the additional porous layers
- the additional porous layers may include the same porous layer above described, namely, the phase-separated polymeric film or may also include a crystallization phase- separated, melt-processible polymer such as described in U S Patent 4,539,256, or a porous layer comprising a liquid-liquid phase-separated, melt-processible polymer as described in U S Patent 4,867,881
- the additional porous layers may be prepared by melt-blending solutions such as described in U S Patent Nos 4,539,256 and 4,867,881, the former describing a melt blend solution of a compound with a crystallization phase-separated, melt-processible polymer and the latter describing
- microporous materials or multi-layer films of the present invention may be employed in any of a wide variety of situations wherein microporous structures may be utilized They find particular utility as battery separators
- Gurley air flow is a measurement of time in seconds required to pass 10 cc of air through a film according to ASTM D 726-58 Method A using a 6 5 mm ⁇ orifice A value of greater than 10,000 sec/ 10 cc is assigned if the Gurley time does not start 15 minutes after the start of the test
- Puncture resistance is a measurement of the peak load required to puncture a perimeter restrained film as in ASTM F- 1306-90
- the specimen clamping fixture holds the sample by compression at the annular region between two circular plates
- the plates provide a 12 7-mm diameter exposed section of film
- the penetration probe is a cylindrical 2-mm diameter probe with a 1-mm radius tip
- the penetration probe is advanced at a rate of 2 mm/s and the maximum load before the film puncture is recorded Values are reported in grams per unit of film thickness
- Porosity is a value calculated from the measured bulk density and polymer density using the following equation
- Porosity (1 - bulk density/polymer density) x 100 The bulk density is determined by dividing the weight of a 47 mm diameter sample containing eight film layers with its thickness and accounting for its area conversion factor
- Tensile Strength Tensile strength at break is a value measured according to ASTM D 882-95a using an InstronTM model 1 122 under the following conditions jaw gap of 25 mm, jaw speed of 500 mm/min, and sample width of 25 mm
- Pore Size This value is the average pore diameter as determined by nitrogen sorption using
- Example 1 In Example 1 and in Comparative Example 1, a normally melt-processable polymer component (high density polyethylene available under the trade designation of HYA-021 from Mobil Chemical Co ) with a melt flow index of 5 0 dg/min (ASTM D1238-90b, Condition F, HLM1) and a weight-average molecular weight of 226,900 was fed into the hopper of a 25 mm twin-screw extaider A compound component, mineral oil (available under a trade designation Amoco White Mineral Oil #31) having a viscosity of 60 centistokes (ASTM D445-96 at 40 °C), was introduced into the extruder through an injection port at a rate to provide a composition of 45 % by weight polymer component and 55 % by weight compound component The polymer and compound component were melt blended in the extruder, and the melt was fed into a coat-hanger die to form a sheet and cast on a cooled wheel to make a 305-micrometer thick film Samples A- H of the cast
- the cast film of Comparative Example 1 was prepared in the same manner as the film of Example 1, except that it was washed under restraint in dichlorotrifluoroethane prior to stretching. Samples C1A-C1H then were cut and stretched in the same manner as the film in Example 1.
- the cast film of Comparative Example C1I was prepared in the same manner as the film of Example 1, except that it was sequentially stretched 3 x 3.
- the cast film of Comparative example C1J was prepared in the same manner as the film of Comparative Example C1I, except that it was washed under restraint in dichlorotrifluroethane prior stretching and was heatset at 1 15 °C for 60 seconds.
- a high density polyethylene identical to that used in Example 1 was fed into a hopper of a 40 mm twin-screw extruder Mineral oil was introduced into the extruder to provide a composition of 40 % by weight polymer component and 60 % by weight blending compound
- the overall flow rate was 1 1 4 kg/hr
- the mixture of polymer and blending compound was maintained at a temperature of 204 °C during the extrusion
- the casting roll was maintained at 66 °C
- the film was stretched 6 x 1 at 104 °C in the machine direction followed by 4 2 x 1 at 1 13 °C in the cross-web direction, followed by continuous washing in dichlorotrifluoroethane and drying
- the sample was tested for thickness, Gurley air flow, puncture resistance, porosity and pore size Thickness was 30 ⁇ m, Gurley was 268 sec/lOcc, puncture resistance was 463 g/25 ⁇ m, porosity was 49 % and pore size was 0 03 ⁇ m
- Example 1 The high density polyethylene used in Example 1 was fed into a hopper of a 40 mm twin-screw extruder A blending compound component (White Mineral Oil #3 1) was introduced into the extruder to provide Composition A having a polymer to compound weight ratio of 35 65
- a second melt-processable polymer component consisting of (1) polypropylene (available as DS 5D45 from Union Carbide) with a melt flow index of 0 65 dg/min (ASTM D 1238-90b, Condition I) and (2) ethylene-hexene copolymer (available from Exxon Chemicals under the trade designation SLP 9057) with a melt flow index 1 2 dg/min (ASTM D1238-90b, Condition E) was dry blended in a weight ratio of 30 70 and fed into the hopper of a 25 mm twin-screw extruder Mineral oil was introduced into the 25 mm extruder to provide Composition B having the same polymer to compound weight ratio of 35 65 A nucleating agent (Millad
- the melt streams from both extruders were combined in a triple manifold die to form a layer of Composition A sandwiched between two layers of Composition B
- the three layer film was cast onto a casting wheel maintained at 77 °C and having a patterned surface with an inverted pyramid shape that provided about 40% contact area with a cast film
- the cast film was oriented 6 5 to 1 in the machine direction at 82 °C, then 4 to 1 in the cross direction at 82 °C
- the oriented film was then continuously washed in dichlorotrifluoroethane
- the resulting film was tested for thickness, Gurley air flow and puncture resistance Thickness was 20 ⁇ m, Gurley was 10 sec/lOcc and puncture resistance was 454 g/25 ⁇ m
- Example 4 The microporous film of Example 4 was made in a manner similar to that of Example 2 except the polymer component was different and some equipment and processing conditions were changed
- the melt-proccessable polymer component was DS5D45 polypropylene
- the flow rates were adjusted to obtain a weight ratio of polymer component to blending compound of 35 65 A nucleating agent (MilladTM 3905) in the amount of 0 09 parts per 100 parts composition was also added to the extruder
- the die was 24 1 mm wide and a water bath maintained at 16 °C was used to quench the cast film instead of a chill roll
- the overall feed rate was 22 7 kg/hr, the extruder was heated to 266 °C to melt the polymer component and maintained at 188 °C while the components were mixed
- the machine direction orientation was 5 x 1 at 121 °C and the cross- web orientation was 4 7 x 1 at 121 °C
- the film was tested for thickness, Gurley air flow, puncture resistance, poros
- Example 5 A microporous film was made to illustrate the effect of a different type of polymer component and blending compound on film properties
- Example 5 The microporous film of Example 5 was made in a manner similar to that of Example 1 except some materials and equipment were different and the process conditions were changed
- the polymer component was composed of a 30 70 by weight blend of two melt processable polymers, polypropylene (DS5D45) and ethylene-hexene copolymer
- Thickness was 1 1 ⁇ m
- Gurley was 802 sec/lOcc
- puncture resistance was 687 g/25 ⁇ m
- Example 6 The microporous film of Example 6 was made in a manner similar to that of Example 5 except some materials were different and the process conditions were changed
- the normally melt processable polymer component was linear low density polyethylene (available under the trade designation DowlexTM 2038) with a melt flow index of 1 0 dg/min (ASTM D1238-90b, Condition I) and no nucleating agent was used
- the film was stretched while at a temperature of 1 10 °C
- Gurley air flow and puncture resistance Thickness was 10 ⁇ m
- Gurley was 425 sec/10 cc
- puncture resistance was 435 g/25 ⁇ m
- Example 7 A microporous film was made to illustrate a liquid/liquid phase separation mechanism
- Example 7 The microporous film of Example 7 was made in a manner similar to that of Example 5 except some materials were different and the process conditions were changed
- the polymer component was composed of a 60 40 by weight blend of two melt processable polymers, polypropylene (DS5D45) and ethylene-hexene copolymer (SLP 9057)
- the compatible liquid was composed 70 30 by weight mixture of mineral oil and PEG 400 dilaurate The flow rates were adjusted to obtain a weight ratio of polymer component to compatible liquid of 30 70
- the film was stretched 5 by 5 simultaneously while at a temperature of 90 °C and washed under restraint in dichlorotrifluoroethane and dried The resulting film was tested for thickness, Gurley air flow and puncture resistance
- Thickness was 8 ⁇ m
- Gurley was 218 sec/1 Occ
- puncture resistance was 473 g/25 ⁇ m
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19990932215 EP1105436B1 (en) | 1998-08-14 | 1999-07-01 | Puncture-resistant polyolefin membranes |
JP2000565038A JP4755339B2 (en) | 1998-08-14 | 1999-07-01 | Fracture resistant polyolefin membrane |
DE1999611624 DE69911624T2 (en) | 1998-08-14 | 1999-07-01 | PERFORATION-RESISTANT POLYOLEFINE MEMBRANES |
KR1020017001861A KR20010072452A (en) | 1998-08-14 | 1999-07-01 | Puncture-Resistant Polyolefin Membranes |
CA 2338549 CA2338549A1 (en) | 1998-08-14 | 1999-07-01 | Puncture-resistant polyolefin membranes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/134,142 US6096213A (en) | 1998-08-14 | 1998-08-14 | Puncture-resistant polyolefin membranes |
US09/134,142 | 1998-08-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000009597A1 true WO2000009597A1 (en) | 2000-02-24 |
Family
ID=22461961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/015085 WO2000009597A1 (en) | 1998-08-14 | 1999-07-01 | Puncture-resistant polyolefin membranes |
Country Status (7)
Country | Link |
---|---|
US (1) | US6096213A (en) |
EP (1) | EP1105436B1 (en) |
JP (1) | JP4755339B2 (en) |
KR (1) | KR20010072452A (en) |
CA (1) | CA2338549A1 (en) |
DE (1) | DE69911624T2 (en) |
WO (1) | WO2000009597A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001016229A1 (en) * | 1999-08-30 | 2001-03-08 | 3M Innovative Properties Company | Capillary collapse resistant microporous material and method |
WO2005035641A1 (en) * | 2003-09-12 | 2005-04-21 | 3M Innovative Properties Company | Microporous pvdf films and method of manufacturing |
JP2005516764A (en) * | 2002-02-12 | 2005-06-09 | ユー・エス・フィルター・ウェイストウォーター・グループ・インコーポレイテッド | Halar film |
WO2007035188A2 (en) * | 2005-03-29 | 2007-03-29 | 3M Innovative Properties Company | Oxidatively stable microlayers of gas diffusion layers |
WO2010071764A1 (en) * | 2008-12-19 | 2010-06-24 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
WO2010096601A1 (en) | 2009-02-20 | 2010-08-26 | Tredegar Film Products Corporation | Hydrophilic apertured formed film |
EP2444453A1 (en) * | 2009-06-19 | 2012-04-25 | Mitsubishi Plastics, Inc. | Porous polypropylene film |
CN107406709A (en) * | 2015-03-02 | 2017-11-28 | 旭硝子株式会社 | Powder coating composition, powder coating and coated article |
Families Citing this family (89)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1736234A3 (en) | 1996-12-20 | 2007-06-13 | Siemens Water Technologies Corp. | Method for scouring fouled membranes |
US20020132107A1 (en) * | 1998-05-15 | 2002-09-19 | O'brien Jeffrey James | Porous polyethylene membrane |
US6773797B1 (en) * | 1998-12-29 | 2004-08-10 | Kimberly-Clark Worldwide, Inc. | Extruded poly (ethylene oxide) and filler composites and films having enhanced ductility and breathability |
TW581709B (en) | 1999-10-22 | 2004-04-01 | Asahi Kasei Corp | Heat-resistant microporous film |
US6432586B1 (en) | 2000-04-10 | 2002-08-13 | Celgard Inc. | Separator for a high energy rechargeable lithium battery |
AUPR143400A0 (en) * | 2000-11-13 | 2000-12-07 | Usf Filtration And Separations Group Inc. | Modified membranes |
AUPR421501A0 (en) | 2001-04-04 | 2001-05-03 | U.S. Filter Wastewater Group, Inc. | Potting method |
AUPR584301A0 (en) * | 2001-06-20 | 2001-07-12 | U.S. Filter Wastewater Group, Inc. | Membrane polymer compositions |
WO2002103835A1 (en) * | 2001-06-20 | 2002-12-27 | Koninklijke Philips Electronics N.V. | Method of manufacturing a lithium battery as well as a lithium battery |
EP1413350B1 (en) * | 2001-08-01 | 2011-12-14 | Asahi Kasei Medical Co., Ltd. | Multilayer microporous film |
AUPR692401A0 (en) | 2001-08-09 | 2001-08-30 | U.S. Filter Wastewater Group, Inc. | Method of cleaning membrane modules |
US20030104236A1 (en) * | 2001-12-03 | 2003-06-05 | Celgard Inc. | Diffusion membrane |
US7140495B2 (en) * | 2001-12-14 | 2006-11-28 | 3M Innovative Properties Company | Layered sheet construction for wastewater treatment |
AUPS300602A0 (en) | 2002-06-18 | 2002-07-11 | U.S. Filter Wastewater Group, Inc. | Methods of minimising the effect of integrity loss in hollow fibre membrane modules |
WO2004029149A1 (en) * | 2002-09-27 | 2004-04-08 | Ferro Corporation | Impact modified thermoplastic olefin compositions |
US7938966B2 (en) | 2002-10-10 | 2011-05-10 | Siemens Water Technologies Corp. | Backwash method |
EP1552878A4 (en) * | 2002-10-18 | 2006-03-22 | Asahi Kasei Pharma Corp | Microporous hydrophilic membrane |
AU2002953111A0 (en) | 2002-12-05 | 2002-12-19 | U. S. Filter Wastewater Group, Inc. | Mixing chamber |
US7207732B2 (en) * | 2003-06-04 | 2007-04-24 | Corning Incorporated | Coated optical fiber and curable compositions suitable for coating optical fiber |
US7462494B2 (en) * | 2003-06-09 | 2008-12-09 | 3M Innovative Properties Company | Method for laser desorption mass spectrometry using porous polymeric substrates with particle fillers |
AU2003903507A0 (en) | 2003-07-08 | 2003-07-24 | U. S. Filter Wastewater Group, Inc. | Membrane post-treatment |
NZ545206A (en) | 2003-08-29 | 2009-03-31 | Siemens Water Tech Corp | Backwash |
DE10348876B4 (en) * | 2003-10-21 | 2014-04-03 | Jnc Corporation | Porous polyolefin membrane |
NZ546959A (en) | 2003-11-14 | 2008-03-28 | Siemens Water Tech Corp | Improved cleaning method for a porous membrane filtration module |
WO2005092799A1 (en) | 2004-03-26 | 2005-10-06 | U.S. Filter Wastewater Group, Inc. | Process and apparatus for purifying impure water using microfiltration or ultrafiltration in combination with reverse osmosis |
CN101426565B (en) | 2004-04-22 | 2012-04-18 | 西门子工业公司 | Filtration apparatus comprising a membrane bioreactor and a treatment vessel for digesting organic materials |
US7332531B2 (en) * | 2004-06-11 | 2008-02-19 | Sk Corporation | Microporous high density polyethylene film |
WO2006002469A1 (en) | 2004-07-02 | 2006-01-12 | U.S. Filter Wastewater Group, Inc | Gas transfer membrane |
US8524794B2 (en) | 2004-07-05 | 2013-09-03 | Siemens Industry, Inc. | Hydrophilic membranes |
US20060008636A1 (en) * | 2004-07-06 | 2006-01-12 | Lee Young K | Microporous polyethylene film and method of producing the same |
US7435761B2 (en) * | 2004-07-06 | 2008-10-14 | Sk Energy Co., Ltd. | Microporous polyethylene film and method of producing the same |
EP1789164B1 (en) | 2004-08-20 | 2013-07-03 | Siemens Industry, Inc. | Square mbr manifolding system |
JP5052135B2 (en) * | 2004-08-30 | 2012-10-17 | 旭化成イーマテリアルズ株式会社 | Polyolefin microporous membrane and battery separator |
CA2579168C (en) | 2004-09-07 | 2015-06-23 | Siemens Water Technologies Corp. | Membrane filtration with reduced volume cleaning step |
CN101039739B (en) | 2004-09-14 | 2014-10-08 | 伊沃夸水处理技术有限责任公司 | Methods and apparatus for removing solids from a membrane module |
WO2006029465A1 (en) | 2004-09-15 | 2006-03-23 | Siemens Water Technologies Corp. | Continuously variable aeration |
CA2588675A1 (en) | 2004-12-03 | 2006-06-08 | Siemens Water Technologies Corp. | Membrane post treatment |
US8758622B2 (en) | 2004-12-24 | 2014-06-24 | Evoqua Water Technologies Llc | Simple gas scouring method and apparatus |
SG150505A1 (en) | 2004-12-24 | 2009-03-30 | Siemens Water Tech Corp | Cleaning in membrane filtration systems |
KR100943697B1 (en) * | 2005-04-06 | 2010-02-23 | 에스케이에너지 주식회사 | Microporous polyethylene film having excellent physical properties, productivity and quality consistency, and method for preparing the same |
CA2605757A1 (en) | 2005-04-29 | 2006-11-09 | Siemens Water Technologies Corp. | Chemical clean for membrane filter |
US7666494B2 (en) * | 2005-05-04 | 2010-02-23 | 3M Innovative Properties Company | Microporous article having metallic nanoparticle coating |
US20070092705A1 (en) * | 2005-06-18 | 2007-04-26 | Young-Keun Lee | Microporous polyethylene film through liquid-liquid phase separation mechanism and preparing method thereof |
KR100943234B1 (en) * | 2005-05-16 | 2010-02-18 | 에스케이에너지 주식회사 | Microporous polyethylene film through liquid-liquid phase separation mechanism and preparing method thereof |
US7628187B2 (en) | 2005-06-13 | 2009-12-08 | Margo Annette Mittelstaedt | Carrying bag with overskirt |
CA2614498A1 (en) | 2005-07-14 | 2007-01-18 | Siemens Water Technologies Corp. | Monopersulfate treatment of membranes |
SG140229A1 (en) | 2005-08-22 | 2008-03-28 | Siemens Water Tech Corp | An assembly for water filtration using a tube manifold to minimise backwash |
WO2007044415A2 (en) | 2005-10-05 | 2007-04-19 | Siemens Water Technologies Corp. | Method and apparatus for treating wastewater |
KR100961660B1 (en) * | 2005-12-21 | 2010-06-09 | 에스케이에너지 주식회사 | Microporous film of semicrystalline polymer and method for preparing the same |
US10615388B2 (en) | 2006-03-22 | 2020-04-07 | Celgard, Llc | Membrane made of a blend of UHMW polyolefins |
US8293098B2 (en) | 2006-10-24 | 2012-10-23 | Siemens Industry, Inc. | Infiltration/inflow control for membrane bioreactor |
US7872086B2 (en) * | 2008-01-17 | 2011-01-18 | Tonen Chemical Corporation | Polymeric material and its manufacture and use |
US8372545B2 (en) | 2007-03-05 | 2013-02-12 | Advanced Membrane Systems, Inc. | Separator for non-aqueous lithium-ion battery |
US8304113B2 (en) * | 2007-03-05 | 2012-11-06 | Advanced Membrane Systems, Inc. | Polyolefin and ceramic battery separator for non-aqueous battery applications |
US8318028B2 (en) | 2007-04-02 | 2012-11-27 | Siemens Industry, Inc. | Infiltration/inflow control for membrane bioreactor |
US9764288B2 (en) | 2007-04-04 | 2017-09-19 | Evoqua Water Technologies Llc | Membrane module protection |
EP3395433A1 (en) | 2007-05-29 | 2018-10-31 | Evoqua Water Technologies LLC | Membrane cleaning with pulsed airlift pump |
RU2478419C2 (en) * | 2007-12-18 | 2013-04-10 | Базелль Полиолефин Италия С.Р.Л. | Membranes |
US20090226813A1 (en) | 2008-03-07 | 2009-09-10 | Kotaro Takita | Microporous Membrane, Battery Separator and Battery |
JP2013500144A (en) | 2008-07-24 | 2013-01-07 | シーメンス インダストリー インコーポレイテッド | Method and filtration system for providing structural support to a filtration membrane module array in a filtration system |
CA2734796A1 (en) | 2008-08-20 | 2010-02-25 | Siemens Water Technologies Corp. | Improved membrane system backwash energy efficiency |
JP5736364B2 (en) * | 2009-03-19 | 2015-06-17 | アムテック リサーチ インターナショナル エルエルシー | Self-supporting, heat-resistant microporous film for use in energy storage devices |
AU2010101488B4 (en) | 2009-06-11 | 2013-05-02 | Evoqua Water Technologies Llc | Methods for cleaning a porous polymeric membrane and a kit for cleaning a porous polymeric membrane |
US8951677B2 (en) | 2009-06-19 | 2015-02-10 | Toray Battery Separator Film Co., Ltd. | Microporous membranes, methods for making such membranes, and the use of such membranes as battery separator film |
JP5728473B2 (en) | 2009-06-19 | 2015-06-03 | 東レバッテリーセパレータフィルム株式会社 | Multilayer microporous film |
WO2010145770A1 (en) * | 2009-06-20 | 2010-12-23 | Treofan Germany Gmbh & Co. Kg | Microporous foil for batteries having shutdown function |
CN102762285B (en) | 2009-08-03 | 2016-06-08 | 索尔维特殊聚合物意大利有限公司 | For the method preparing ethylene/CTFE thin polymer film |
ES2738898T3 (en) | 2010-04-30 | 2020-01-27 | Evoqua Water Tech Llc | Fluid flow distribution device |
CN103816808B (en) | 2010-06-07 | 2017-01-11 | 3M创新有限公司 | Filtration methods and devices |
WO2012040412A1 (en) | 2010-09-24 | 2012-03-29 | Siemens Industry, Inc. | Fluid control manifold for membrane filtration system |
KR20140053096A (en) | 2011-06-16 | 2014-05-07 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Microporous materials with fibrillar mesh structure and methods of making and using the same |
SG11201401089PA (en) | 2011-09-30 | 2014-04-28 | Evoqua Water Technologies Llc | Improved manifold arrangement |
KR20140097140A (en) | 2011-09-30 | 2014-08-06 | 에보쿠아 워터 테크놀로지스 엘엘씨 | Isolation valve |
TWI453114B (en) * | 2012-05-11 | 2014-09-21 | Entire Technology Co Ltd | Manufacturing method for porous composite film |
US8460829B1 (en) * | 2012-05-17 | 2013-06-11 | GM Global Technology Operations LLC | Porous polymer separator layer having a non-uniform cross-sectional thickness for use in a secondary liquid-electrolyte battery |
AU2013280452B2 (en) | 2012-06-28 | 2017-07-20 | Evoqua Water Technologies Llc | A potting method |
EP2895257A1 (en) | 2012-09-14 | 2015-07-22 | Evoqua Water Technologies LLC | A polymer blend for membranes |
US9962865B2 (en) | 2012-09-26 | 2018-05-08 | Evoqua Water Technologies Llc | Membrane potting methods |
US9764289B2 (en) | 2012-09-26 | 2017-09-19 | Evoqua Water Technologies Llc | Membrane securement device |
EP2900356A1 (en) | 2012-09-27 | 2015-08-05 | Evoqua Water Technologies LLC | Gas scouring apparatus for immersed membranes |
AU2014329869B2 (en) | 2013-10-02 | 2018-06-14 | Evoqua Water Technologies Llc | A method and device for repairing a membrane filtration module |
JP2017535925A (en) | 2014-11-26 | 2017-11-30 | セルガード エルエルシー | Improved multilayer microporous separator for lithium ion secondary batteries and related methods |
CN112234315A (en) | 2014-11-26 | 2021-01-15 | 赛尔格有限责任公司 | Microporous membrane separator for lithium ion rechargeable batteries and related methods |
US10322375B2 (en) | 2015-07-14 | 2019-06-18 | Evoqua Water Technologies Llc | Aeration device for filtration system |
PL3375026T3 (en) | 2015-11-11 | 2022-11-21 | Celgard, Llc | Microlayer membranes, improved battery separators, and methods of manufacture and use |
CN105617892B (en) * | 2015-12-28 | 2018-03-27 | 贵州省材料产业技术研究院 | The preparation method of the hydrophilic polymer-modified composite hollow fiber membrane of resistance to chlorination |
US20170222205A1 (en) * | 2016-01-29 | 2017-08-03 | Celgard, Llc | Separators, batteries, systems, vehicles, and related methods |
KR20190062535A (en) * | 2016-10-24 | 2019-06-05 | 스미또모 가가꾸 가부시키가이샤 | A secondary battery including a separator and a separator |
CN112563659B (en) * | 2019-09-26 | 2023-05-05 | 中国石油化工股份有限公司 | Polypropylene microporous membrane and preparation method and application thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4247498A (en) | 1976-08-30 | 1981-01-27 | Akzona Incorporated | Methods for making microporous products |
US4539256A (en) | 1982-09-09 | 1985-09-03 | Minnesota Mining And Manufacturing Co. | Microporous sheet material, method of making and articles made therewith |
US4726989A (en) | 1986-12-11 | 1988-02-23 | Minnesota Mining And Manufacturing | Microporous materials incorporating a nucleating agent and methods for making same |
US4867881A (en) | 1987-09-14 | 1989-09-19 | Minnesota Minning And Manufacturing Company | Orientied microporous film |
US5051183A (en) | 1989-08-03 | 1991-09-24 | Tonen Corporation | Microporous polyolefin membrane and method of producing same |
EP0603500A1 (en) * | 1992-12-21 | 1994-06-29 | Mitsubishi Chemical Corporation | Porous film or sheet, battery separator and lithium battery |
EP0767200A2 (en) * | 1995-10-05 | 1997-04-09 | Mitsubishi Chemical Corporation | High-strength porous film and process for producing the same |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5238623A (en) * | 1989-11-20 | 1993-08-24 | Minnesota Mining And Manufacturing Company | Method for preparing microporous polyolefin shaped articles |
DE69424569T2 (en) * | 1993-01-25 | 2001-01-18 | Daikin Ind Ltd | Porous film made of polytetrafluoroethylene |
TW408134B (en) * | 1995-07-18 | 2000-10-11 | Mitsui Chemicals Inc | Microporous film of high molecular weight polyolefin and process for producing same |
JPH09169867A (en) * | 1995-10-17 | 1997-06-30 | Asahi Chem Ind Co Ltd | Microporous film and its production |
KR100257359B1 (en) * | 1995-12-05 | 2000-05-15 | 야마모토 카즈모토 | Microporous polyethylene membranes having low fusing temperatures |
TW412542B (en) * | 1995-12-25 | 2000-11-21 | Asahi Chemical Ind | Short-resistant micro-porous polyethylene membrane |
-
1998
- 1998-08-14 US US09/134,142 patent/US6096213A/en not_active Expired - Lifetime
-
1999
- 1999-07-01 CA CA 2338549 patent/CA2338549A1/en not_active Abandoned
- 1999-07-01 EP EP19990932215 patent/EP1105436B1/en not_active Expired - Lifetime
- 1999-07-01 KR KR1020017001861A patent/KR20010072452A/en not_active Application Discontinuation
- 1999-07-01 JP JP2000565038A patent/JP4755339B2/en not_active Expired - Fee Related
- 1999-07-01 DE DE1999611624 patent/DE69911624T2/en not_active Expired - Lifetime
- 1999-07-01 WO PCT/US1999/015085 patent/WO2000009597A1/en not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4247498A (en) | 1976-08-30 | 1981-01-27 | Akzona Incorporated | Methods for making microporous products |
US4539256A (en) | 1982-09-09 | 1985-09-03 | Minnesota Mining And Manufacturing Co. | Microporous sheet material, method of making and articles made therewith |
US4726989A (en) | 1986-12-11 | 1988-02-23 | Minnesota Mining And Manufacturing | Microporous materials incorporating a nucleating agent and methods for making same |
US4867881A (en) | 1987-09-14 | 1989-09-19 | Minnesota Minning And Manufacturing Company | Orientied microporous film |
US5051183A (en) | 1989-08-03 | 1991-09-24 | Tonen Corporation | Microporous polyolefin membrane and method of producing same |
EP0603500A1 (en) * | 1992-12-21 | 1994-06-29 | Mitsubishi Chemical Corporation | Porous film or sheet, battery separator and lithium battery |
EP0767200A2 (en) * | 1995-10-05 | 1997-04-09 | Mitsubishi Chemical Corporation | High-strength porous film and process for producing the same |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6461724B1 (en) | 1999-08-30 | 2002-10-08 | 3M Innovative Properties Company | Microporous material resistant to capillary collapse |
WO2001016229A1 (en) * | 1999-08-30 | 2001-03-08 | 3M Innovative Properties Company | Capillary collapse resistant microporous material and method |
JP2005516764A (en) * | 2002-02-12 | 2005-06-09 | ユー・エス・フィルター・ウェイストウォーター・グループ・インコーポレイテッド | Halar film |
JP4656839B2 (en) * | 2002-02-12 | 2011-03-23 | シーメンス・ウォーター・テクノロジーズ・コーポレイション | Halar film |
US8663868B2 (en) | 2003-09-12 | 2014-03-04 | 3M Innovative Properties Company | Microporous PVDF films |
WO2005035641A1 (en) * | 2003-09-12 | 2005-04-21 | 3M Innovative Properties Company | Microporous pvdf films and method of manufacturing |
US7338692B2 (en) | 2003-09-12 | 2008-03-04 | 3M Innovative Properties Company | Microporous PVDF films |
US8962214B2 (en) | 2003-09-12 | 2015-02-24 | 3M Innovative Properties Company | Microporous PVDF films |
WO2007035188A2 (en) * | 2005-03-29 | 2007-03-29 | 3M Innovative Properties Company | Oxidatively stable microlayers of gas diffusion layers |
WO2007035188A3 (en) * | 2005-03-29 | 2007-06-07 | 3M Innovative Properties Co | Oxidatively stable microlayers of gas diffusion layers |
US7608334B2 (en) | 2005-03-29 | 2009-10-27 | 3M Innovative Properties Company | Oxidatively stable microlayers of gas diffusion layers |
WO2010071764A1 (en) * | 2008-12-19 | 2010-06-24 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
US10240013B2 (en) | 2008-12-19 | 2019-03-26 | 3M Innovative Properties Company | Microporous material from ethylene-chlorotrifluoroethylene copolymer and method for making same |
WO2010096601A1 (en) | 2009-02-20 | 2010-08-26 | Tredegar Film Products Corporation | Hydrophilic apertured formed film |
EP2444453A4 (en) * | 2009-06-19 | 2012-12-12 | Mitsubishi Plastics Inc | Porous polypropylene film |
EP2444453A1 (en) * | 2009-06-19 | 2012-04-25 | Mitsubishi Plastics, Inc. | Porous polypropylene film |
CN107406709A (en) * | 2015-03-02 | 2017-11-28 | 旭硝子株式会社 | Powder coating composition, powder coating and coated article |
EP3266841A4 (en) * | 2015-03-02 | 2018-12-12 | AGC Inc. | Composition for powder paint, powder paint, and painted article |
CN107406709B (en) * | 2015-03-02 | 2020-06-23 | Agc 株式会社 | Composition for powder coating, and coated article |
Also Published As
Publication number | Publication date |
---|---|
DE69911624D1 (en) | 2003-10-30 |
DE69911624T2 (en) | 2004-07-01 |
US6096213A (en) | 2000-08-01 |
KR20010072452A (en) | 2001-07-31 |
EP1105436B1 (en) | 2003-09-24 |
CA2338549A1 (en) | 2000-02-24 |
JP4755339B2 (en) | 2011-08-24 |
JP2002522610A (en) | 2002-07-23 |
EP1105436A1 (en) | 2001-06-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6096213A (en) | Puncture-resistant polyolefin membranes | |
EP0977801B1 (en) | Temperature-sensitive microporous film | |
EP0273582B1 (en) | Microporous materials incorporating a nucleating agent and methods for making same | |
US4863792A (en) | Multi-layer laminates of microporous films | |
EP0105629B1 (en) | Microporous sheet material, method of making and articles made therewith | |
US4197148A (en) | Process for producing a permeable membrane | |
US4539256A (en) | Microporous sheet material, method of making and articles made therewith | |
US6632850B2 (en) | Microporous materials and methods of making the same | |
JP4494637B2 (en) | Polyolefin microporous membrane and method for producing the same | |
US5051183A (en) | Microporous polyolefin membrane and method of producing same | |
JP3347854B2 (en) | Polyolefin microporous membrane, method for producing the same, battery separator and filter using the same | |
US20140094076A1 (en) | Microporous Materials With Fibrillar Mesh Structure and Methods of Making and Using the Same | |
CA2025520C (en) | Microporous polyolefin membrane and method of producing same | |
KR20000002325A (en) | Process for preparing fine porous film of polyolefine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP KR |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2338549 Country of ref document: CA Ref country code: CA Ref document number: 2338549 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020017001861 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999932215 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1999932215 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020017001861 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1999932215 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1020017001861 Country of ref document: KR |